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# Kinetics of Homogeneous Multistep Reactions

- 1st Edition, Volume 38 - January 25, 2001
- Author: Friedrich G. Helfferich
- Language: English
- Paperback ISBN:9 7 8 - 0 - 4 4 4 - 5 5 1 1 8 - 4
- Hardback ISBN:9 7 8 - 0 - 4 4 4 - 8 2 6 0 6 - 0
- eBook ISBN:9 7 8 - 0 - 0 8 - 0 5 3 5 2 6 - 5

This book addresses primarily the chemist and engineer in industrial research and process development, where competitive pressures put a premium on scale-up by large factors to cut… Read more

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Request a sales quoteThis book addresses primarily the chemist and engineer in industrial research and process development, where competitive pressures put a premium on scale-up by large factors to cut development time. To be safe, such scale-up should be based on "fundamental" kinetics, that is, mathematics that reflect the elementary steps of which the reactions consist. The book forges fundamental kinetics into a practical tool by presenting new effective methods for elucidation of mechanisms and reduction of mathematical complexity without unacceptable sacrifice in accuracy.

**Preface. Introduction. References. Concepts, definitions, conventions, and notation**. Classification of reactions. Steps, pathways, networks, and cycles. Rates. Rate equations and activation energies. Orders, molecularities, and ranks. Conversion, yield, and selectivity. Summary. References.

**Fundamentals**. Statistical basis: molecularities and reaction orders. Nonideality. Temperature dependence. Compilation of rate equations of multistep reactions. Consistency criteria. Summary. References.

**Determination of rates, orders, and rate coefficients**. Research reactors. Analytical support. Reaction orders and apparent rate coefficients. Numerical work-up, error recognition, and reliability. Summary. References.

**Tools for reduction of complexity**. Rate-controlling steps. Quasi-equilibrium steps. Quasi-stationary states: the Bodenstein approximation. Relative abundance in catalysis and polymerization and long-chain approximation. Summary. References.

**Elementary step combinations**. Reversible reactions. Parallel steps. Coupled parallel steps. Sequential steps. Competing steps. Reactions with fast pre-dissociation. General solution for first-order networks. Summary. References.

**Practical mathematics of multistep reactions**. Simple and non-simple pathways and networks. Pseudo-first order rate coefficients. Simple pathways. Simple networks. Non-simple pathways and networks. Summary. References.

**Network elucidation**. Order and rank. "One plus" rate equations. Relationships between network properties and kinetic behavior. Other criteria and guidelines. Auxiliary techniques. Summary. References.

**Homogeneous catalysis**. Single-species catalysis. Complex catalysis. Classical models of enzyme kinetics. General formula for single catalytic cycles: Christiansen mathematics. Reduction of complexity. Relationships between pathway properties and kinetic behavior. Cycles with external reactions. Multiple cycles. Competing reactions (cycles with common members). Dual- and multiple-form catalysts (connected cycles). Reactions with multiple products (cycles with common pathway segments). Self-accelerating reactions (autocatalysis). Analogies to heterogeneous catalysis. Summary. References.

**Chain reactions**. General properties. Initiation. Reactions with two chain carriers: the hydrogen-bromide reaction. Identification of relevant steps. Transmission of reactivity: indirect initiation, chain transfer. Reactions with more than two free radicals. Inhibition and induction periods. Summary. References.

**Polymerization**. Types of polymerization reactions. Step-growth polymerization. Free-radical polymerization. Ionic polymerization. Coordination polymerization. Chain-growth copolymerization. Summary. References.

**Mathematical Modeling**. Strategies of process development. Effective mathematical modeling. "Shortsightedness" of elementary reaction steps. Model validation. Summary. References.

**Unusual thermal and mass-transfer effects**. Anomalous temperature dependence. Uncommon heat-transfer problems. Uncommon mass-transfer problems. Summary. References.

**Glossary of symbols. Author Index. Subject Index.**

- No. of pages: 426
- Language: English
- Edition: 1
- Volume: 38
- Published: January 25, 2001
- Imprint: Elsevier Science
- Paperback ISBN: 9780444551184
- Hardback ISBN: 9780444826060
- eBook ISBN: 9780080535265

FH

### Friedrich G. Helfferich

Affiliations and expertise

Professor Emeritus, Pennsylvania State University, Philadelphia, USARead

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